JPH0770277A - Production of heat-resistant resin - Google Patents

Abstract

PURPOSE:To provide a process for producing a heat-resistant resin capable of producing a polyamide, polyimide or polyamide imide having remarkably small polydisperse index and high molecular weight to give a molded article having excellent mechanical properties. CONSTITUTION:A polyamide, polyimide or polyamide imide is produced by reacting a diisocyanate with a polybasic carboxylic acid and/or a polybasic carboxylic acid anhydride. In this process for the production of the above heat- resistant resin, the raw material monomers are subjected to condensation reaction in an organic solvent at a monomer concentration of about >=20wt.% and a reaction temperature of about <=150 deg.C (the 1st-stage reaction), the reaction mixture is diluted to a level lower than the monomer concentration in the 1st stage reaction and the molecular weight is increased (the 2nd-stage reaction) at a temperature higher than the reaction temperature of the 1st-stage reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide, a polyimide or a polyamide-imide in which the resulting molded product has remarkably improved mechanical properties.

[0002]

2. Description of the Related Art Diisocyanate and polycarboxylic acid and / or acid anhydride are mixed with 100 to 2 in an organic polar solvent such as N-methyl-2-pyrrolidone or dimethylacetamide.
A method of obtaining a polyamide, a polyimide, or a polyamide-imide by heat-condensing at 00 ° C. for several hours has been conventionally performed.

[0003]

However, when the diisocyanate is heated in the solvent in this manner, the isocyanate causes a side reaction with the solvent molecule. Such side reactions not only hinder the achievement of high molecular weight of the obtained polymer, but also promote the branching / crosslinking reaction of the polymer which adversely affects the mechanical properties of the molded product.

Generally, in the above method, the higher the polymerization temperature is, the higher the molecular weight of the obtained polymer can be made, but at the same time, the side reaction of diisocyanate and the branching / crosslinking reaction of the polymer also proceed. The degree of dispersion is wide. As a result, the mechanical properties of moldings obtained from such polymers are not as high as expected from the number average molecular weight.

The object of the present invention is to suppress the side reaction between an isocyanate and a solvent, which hinders the achievement of high molecular weight, and the branching / cross-linking reaction of the polymer, which adversely affects the mechanical properties of the molded article, and to further increase the molecular weight. Another object of the present invention is to provide a method for producing a polyamide or a polyimide / polyamideimide, in which mechanical properties of the obtained molded product are remarkably improved.

[0006]

[Means for Solving the Problems] The above-mentioned problems are solved by first dissolving a raw material monomer in an organic solvent at a relatively high concentration and condensing it at a relatively low temperature (first-stage reaction) to obtain a reaction mixture obtained. Diluting to a concentration not higher than the monomer concentration of the first-stage reaction and subjecting this to further polycondensation at a temperature not lower than the reaction temperature of the first-stage reaction (second-stage reaction), which is a two-stage reaction in terms of concentration and reaction temperature. Achieved by That is, the present invention relates to a diisocyanate and a polycarboxylic acid and / or
Alternatively, when a polyamide, polyimide or polyamideimide polymer is produced by reacting an acid anhydride of a polyvalent carboxylic acid, the concentration of the raw material monomer is about 2 in the organic solvent.
Condensation is carried out under the condition that the reaction temperature is 0% by weight or more and the reaction temperature is about 150 ° C. or less (first-stage reaction), and then the concentration of the reaction mixture is diluted to the monomer concentration of the first-stage reaction or less, and the reaction temperature of the first-stage reaction is reduced. The present invention relates to a method for producing a heat-resistant resin, which is characterized in that it has a high molecular weight at the above temperature (second stage reaction).

The reaction temperature of the first stage reaction is 150 ° C. or lower,
It is preferably 100 ° C. or lower, more preferably 50 to 10
It is 0 ° C. When the reaction temperature exceeds 150 ° C., the side reaction between the isocyanate and the solvent molecule is promoted, so that the high molecular weight of the polymer cannot be sufficiently achieved during the second step reaction.

The monomer concentration is 20% by weight or more, preferably 20 to 65% by weight, more preferably 40 to 5%.
It is 5% by weight. When the monomer concentration is less than 20% by weight, the molecular weight of the polymer obtained in the first stage reaction is too low,
Even if the second-stage reaction is carried out thereafter, a sufficiently high molecular weight cannot be obtained. On the other hand, when the monomer concentration exceeds 65% by weight, the branching / crosslinking reaction of the polymer may proceed to prevent the polymer from having a sufficiently high molecular weight, or the mechanical properties may be adversely affected.

The molecular weight and molecular weight distribution (polydispersity) of the polymer finally obtained correlate with the molecular weight and molecular weight distribution of the polymer obtained at the end of the first stage reaction. Therefore, the molecular weight (number average molecular weight) of the polymer at the end of the first-step reaction is 3,000 to 25,000, especially 10,000.
Polymers having a polydispersity of 0 to 20,000 and a polydispersity of 1.5 to 3.0, especially 2.0 to 2.5, are well balanced in molecular weight and molecular weight distribution, that is, have excellent mechanical properties. Can be provided.

The temperature of the second-step reaction is higher than the reaction temperature of the first-step reaction. Further, the obtained reaction mixture is diluted with a solvent so that the concentration thereof is equal to or lower than the monomer concentration of the first stage reaction, and the reaction is performed. In particular, the reaction temperature is not lower than the reaction temperature of the first-step reaction and is 100 to 200 ° C., and the reaction mixture concentration is not higher than the monomer concentration of the first-step reaction and is 30% by weight.
It is preferable to make the following adjustments.

The organic solvent used in the production of the polymer of the present invention is mainly dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane and γ-butyrolactone, and cyclohexanone, isophorone and the like. Ketones,
Ethers such as dioxane and tetrahydrofuran, hydrocarbons such as toluene and xylene, nitrile solvents such as propionitrile and acetonitrile, and nitro solvents such as nitromethane and nitroethane can also be used. These are used alone or as a mixed solvent.

In the present invention, the following monomers can be mainly used, but they are not limited to these. First, as the acid component monomer, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid,
Aliphatic dicarboxylic acids such as tetradecanedioic acid, isophthalic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, terephthalic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylmethane-2,4'-dicarboxylic acid, Diphenylmethane-3,4'-dicarboxylic acid, diphenylmethane-3,3'-dicarboxylic acid, 1,2-diphenylethane-4,4'-dicarboxylic acid, 1,2-diphenylethane-2,4'-dicarboxylic acid, 1,2-diphenylethane-3,4'-dicarboxylic acid, 1,2-diphenylethane-3,3'-dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, 2- (2-carboxyphenyl) ) 2- (4-carboxyphenyl) propane, 2- (3-carboxyphenyl) 2- (4-carboxyphenyl) propane, , 2- bis (3-carboxyphenyl) propane, diphenyl ether-4,4
-Dicarboxylic acid, diphenyl ether-2,4-dicarboxylic acid, diphenyl ether-3,4-dicarboxylic acid,
Diphenyl ether-3,3-dicarboxylic acid, diphenyl sulfide-4,4-dicarboxylic acid, diphenyl sulfide-2,4-dicarboxylic acid, diphenyl sulfide-3,4-dicarboxylic acid, diphenyl sulfide-3,
3-dicarboxylic acid, diphenylsulfone-4,4-dicarboxylic acid, diphenylsulfone-2,4-dicarboxylic acid, diphenylsulfone-3,4-dicarboxylic acid, diphenylsulfone-3,3-dicarboxylic acid, benzophenone-4,4 -Dicarboxylic acid, benzophenone-2,4-
Dicarboxylic acid, benzophenone-3,4-dicarboxylic acid, benzophenone-3,3-dicarboxylic acid, 1,1,
3-trimethyl-5-carboxy-3- (p-carboxyphenyl) indane, pyridine-2,6-dicarboxylic acid, bis [(4-carboxy) phthalimide] -4,
4'-diphenyl ether, bis [(4-carboxy)
Phthalimide] -aromatic dicarboxylic acid such as α, α'-metaxylene, trimellitic acid, butane-1,2,4-
Tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid and their anhydrides, butane-1,2,3,4-
Tetracarboxylic acid, cyclobutane-1,2,3,4-tetracarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid (pyromet acid), benzophenone-3,
3 ', 4,4'-tetracarboxylic acid, diphenyl ether-3,3', 4,4'-tetracarboxylic acid, benzene-1,2,3,4-tetracarboxylic acid, biphenyl-
3,3 ', 4,4'-tetracarboxylic acid, biphenyl-
2,2 ', 3,3'-tetracarboxylic acid, naphthalene-
2,3,6,7-tetracarboxylic acid, naphthalene-1,
2,4,5-tetracarboxylic acid, naphthalene-1,4
5,8-Tetracarboxylic acid, decahydronaphthalene-
1,4,5,8-Tetracarboxylic acid, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-
1,2,5,6-tetracarboxylic acid, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid, 2,
7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid, 2,3,6,7-tetrachloronaphthalene-
1,4,5,8-tetracarboxylic acid, phenanthrene-
1,3,9,10-tetracarboxylic acid, perylene-3,
4,9,10-tetracarboxylic acid, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) methane, 1,1-bis (2,3-dicarboxyphenyl) ethane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 2,2-bis (2,3-dicarboxyphenyl) propane, 2,3-bis (3,4-)
Dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, cyclopentane-1,2,
3,4-tetracarboxylic acid, pyrrolidine-2,3,4
5-tetracarboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic acid, ethylene glycol bis (ane Hydrotrimeritate), propylene glycol bis (anhydrotrimeritate) and dianhydrides thereof. These are used alone or as a mixture of two or more kinds.

As the isocyanate component, for example, 4,4'-diphenylmethane diisocyanate,
2,4-Tolylene diisocyanate, 2,6-Tolylene diisocyanate, o-Tolidine diisocyanate, p
-Phenylene diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate,
4,4'-diphenyl ether diisocyanate, m-
Examples include xylene diisocyanate, p-xylene diisocyanate, 4,4′-methylenebis (cyclohexyl diisocyanate), isophorone diisocyanate, hexamethylene diisocyanate, and the like. These are used alone or as a mixture of two or more kinds.

According to the method of the present invention, the acid component and the isocyanate component are in a molar ratio of acid component / isocyanate component =
100 / 110-110 / 100, preferably 100 /
Charge and react at a ratio of 100.

Further, in the present invention, the reaction is a catalyst for the reaction between isocyanate and an active hydrogen compound, for example, tertiary amines, alkali metal compounds, alkaline earth metal compounds, metals such as cobalt, titanium, tin and zinc, It may be carried out in the presence of an antimetal compound or the like. Even when the production method of the present invention is carried out in the presence of a catalyst, the effect of the two-step reaction can be sufficiently exhibited, and a polymer having a higher molecular weight and a narrower molecular weight distribution can be obtained as compared with the conventional method.

In the present invention, as the diisocyanate, o
A polyamide, a polyimide or a polyamideimide obtained by essentially using tolidine diisocyanate is preferable.

The polymers obtained according to the invention are GP
The number average molecular weight (Mn) measured by C is about 3,000.
0 to 150,000, preferably 60,000 to 20
And the polydispersity (Mw / Mn) is approximately 1.5 to 4.5, preferably 2.0 to 4.0.
That is, it is possible to obtain a polymer having a higher molecular weight and a smaller polydispersity than those obtained by conventional methods.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0019]

EXAMPLES The physical properties of the polymer or film produced in each example were measured by the methods described below. 1. Logarithmic viscosity (dl / g) Relative viscosity was measured at a temperature of 25 ° C. for a dilute solution in which 0.5 g of the polymer was dissolved in 100 ml of N-methyl-2-pyrrolidone, and the relative viscosity was calculated from the following formula. Logarithmic viscosity = ln ηrel / C (wherein ηrel represents relative viscosity and C represents the concentration of the polymer solution). Molecular weight (Mn: number average molecular weight, Mw: weight average molecular weight) It was measured by the following method by the GPC method. i) Column: shodex [Showa Denko KK] AD80
0P, AD805 / S, AD804 / S, AD803 /
S and AD802 / S were connected in series. ii) Mobile phase: N in which 0.1% by weight of lithium bromide was dissolved
-Methyl-2-pyrrolidone iii) Standard: polystyrene with the following molecular weight (Mn) was used. 1. 6,770,000 2. 2,870,000 3. 1,260,000 4. 355,000 5. 102,000 6. 43,900 7. 9,500 8. 5,400 9. 2,800 iv) device: Automatic sampler [Shimadzu Corporation, SCL6
A] Pump [LC6A manufactured by Shimadzu Corporation] Data conversion system [CR-4A manufactured by Shimadzu Corporation] Deflection meter [SE-51 manufactured by Showa Denko KK] 3. Tensile strength (kg / mm ² ), tensile elongation (%) and elastic modulus (kg / mm ² ) according to JIS-C-2318. 4. Glass transition temperature (Tg) (° C.) According to TMA tensile measurement method. Load: 1 g, sample size: 5 × 20 mm Temperature rising temperature: measured at 10 ° C./min. Example 1 The following polymerization components were charged in a reaction vessel, and reacted under nitrogen atmosphere with stirring at 70 ° C. for about 2 hours and at 100 ° C. for about 3 hours (first stage reaction). Polymerization component trimellitic anhydride 192 g o-trizine diisocyanate 211 g 4,4′-diphenylmethane diisocyanate 50 g N-methyl-2-pyrrolidone (distilled) 365 g Then, 1 liter of N-methyl-2-pyrrolidone was added, and about 2 Temperature rises to 200 ℃ over time
The reaction was stopped by stirring at C for about 1 hour (second stage reaction).
The polymer solution thus obtained was cast-coated on a releasable polyester film having a thickness of 100 μm so that the thickness after drying would be 30 μm, dried at 100 ° C. for 5 minutes and at 150 ° C. for 30 minutes, Peeled from the film. Then, in order to completely remove the solvent, the mixture was heated at 200 ° C. under reduced pressure for about 3 hours. Table 1 shows various physical properties of the thus obtained polymer and polymer film.

Example 2 A polymer was obtained in the same manner as in Example 1 except that the polymerization components in the first-stage reaction were changed as follows, and a film was produced. Polymerization component trimellitic anhydride 154 g 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride 65 g o-tolidine diisocyanate 264 g N-methyl-2-pyrrolidone (distilled) 395 g of the obtained polymer and film Table 1 shows various physical properties.

Example 3 A polymer was obtained in the same manner as in Example 1 except that the polymerization components in the first-stage reaction were changed as follows, and a film was further produced. Polymerization component trimellitic anhydride 192 g 2,4-tolylene diisocyanate 35 g o-tolidine diisocyanate 264 g N-methyl-2-pyrrolidone (distilled) 450 g Table 1 shows various physical properties of the obtained polymer and film.

Example 4 A polymer was obtained in the same manner as in Example 1 except that the polymerization components in the first stage reaction were changed as follows, and a film was further produced. Polymerization component Isophthalic acid 83 g Terephthalic acid 83 g o-Tolidine diisocyanate 264 g N-methyl-2-pyrrolidone (distilled) 418 g Various physical properties of the obtained polymer and film are shown in Table 1.

Example 5 A polymer was obtained in the same manner as in Example 1 except that the polymerization components in the first-step reaction were changed as follows, and a film was produced. Polymerization component Isophthalic acid 166 g o-Tolidine diisocyanate 264 g 2,4-Tolylene diisocyanate 35 g N-methyl-2-pyrrolidone (distilled) 460 g Table 1 shows various physical properties of the obtained polymer and film.

Example 6 The following polymerization components were charged in a reaction vessel and reacted at 50 ° C. for about 6 hours under stirring in a nitrogen atmosphere (first stage reaction). Polymerization component trimellitic anhydride 192 g 4,4'-diphenylmethane diisocyanate 250 g sodium methylate 0.5 g N-methyl-2-pyrrolidone (distilled) 350 g Then, 1 liter of N-methyl-2-pyrrolidone was added, and about. The temperature is raised to 140 ° C over 30 minutes and then 140
The reaction was stopped by stirring at C for about 3 hours (second stage reaction).
A film was obtained from the obtained polymer solution in the same manner as in Example 1. Table 1 shows various physical properties of the thus obtained polymer and polymer film.

Example 7 A polymer was obtained in the same manner as in Example 6 except that the polymerization components in the first-stage reaction were changed as follows, and a film was further produced. Polymerization component trimellitic anhydride 192 g o-trizine diisocyanate 211 g 4,4'-diphenylmethane diisocyanate 50 g triethylenediamine 10 g N-methyl-2-pyrrolidone (distilled) 350 g Various physical properties of the obtained polymer and film are shown in Table 1. Show.

[0026]

[Table 1]

[0027]

Industrial Applicability According to the present invention, a polyamide, polyimide or polyamideimide having a very low polydispersity and a high molecular weight can be produced, whereby a molded article having excellent mechanical properties can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideo Nishino 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd.

Claims (11)

[Claims] 1. When producing a polyamide, polyimide or polyamideimide polymer by reacting a diisocyanate with a polyvalent carboxylic acid and / or an acid anhydride of a polyvalent carboxylic acid, the concentration of the raw material monomer in an organic solvent is about Condensation is carried out under the conditions of 20% by weight or more and the reaction temperature is about 150 ° C. or less (first stage reaction), and then the reaction mixture concentration is diluted to be not more than the monomer concentration of the first stage reaction so that the reaction temperature is not less than the reaction temperature of the first stage reaction. A method for producing a heat-resistant resin, which comprises increasing the molecular weight at a temperature (second stage reaction). 2. The method for producing a heat-resistant resin according to claim 1, wherein the reaction temperature of the first stage reaction is 100 ° C. or lower. 3. The reaction temperature of the first stage reaction is 50 to 100 ° C.
The method for producing a heat-resistant resin according to claim 2, wherein 4. The monomer concentration in the first stage reaction is 20 to 65.
The method for producing a heat-resistant resin according to claim 1, wherein the heat-resistant resin is in a weight percentage. 5. The monomer concentration in the first stage reaction is 40 to 55.
The method for producing a heat-resistant resin according to claim 4, wherein the heat-resistant resin is in a weight percentage. 6. The number average molecular weight of the polymer at the end of the first stage reaction is 3,000 to 25,000 and the polydispersity is 1.5.
It is-3.0, The manufacturing method of the heat resistant resin of Claim 1 characterized by the above-mentioned. 7. The reaction temperature of the second stage reaction is 100 to 200.
The method for producing a heat-resistant resin according to claim 1, wherein the temperature is ° C. 8. The method for producing a heat-resistant resin according to claim 1, wherein the concentration of the reaction mixture in the second stage reaction is 30% by weight or less. 9. The number average molecular weight of the polymer after the completion of the second-stage reaction is 60,000 or more, and the polydispersity is 1.5 to 4.5.
The method for producing a heat-resistant resin according to claim 1, wherein 10. The method for producing a heat resistant resin according to claim 1, wherein the reaction is carried out in the presence of a catalyst for the reaction between the isocyanate and the active hydrogen compound. 11. The method for producing a heat-resistant resin according to claim 1, wherein o-tolidine diisocyanate is essential as the diisocyanate.